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Cite This: Chem. Mater. 2017, 29, 9565-9571
Tl2Ag12Se7: A New pnp Conduction Switching Material with Extraordinarily Low Thermal Conductivity Yixuan Shi, Abdeljalil Assoud, Cheriyedath Raj Sankar,† and Holger Kleinke* Department of Chemistry and Waterloo Institute for Nanotechnology, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 S Supporting Information *
ABSTRACT: While continuing our investigations of thallium chalcogenides because of their outstanding thermoelectric properties, we discovered a new selenide with an interesting pnp switching behavior around 400 K. Tl2Ag12Se7 was prepared via high temperature reaction from the elements in the stoichiometric ratio. This selenide crystallizes in a new structure type, namely a √3 × √3 × 1 super cell of the Zr2Fe12P7 type, adopting space group P3̅, a = b = 18.9153(18) Å, c = 4.3783(4) Å, and V = 1356.6(2) Å3 (Z = 3). The structure consists of a complex network of three-dimensionally connected AgSe4 tetrahedra that include linear channels filled with thallium atoms. This material is a semiconductor with an experimentally derived activation gap of 0.8 eV and extraordinarily low thermal conductivity of 4 Å along the c axis. These Tl−Se distances are typical for thallium selenides, which often also comprise Tl−Tl contacts shorter than 3.7 Å.15 The lack of such secondary contacts is likely a consequence of the small Tl content of less than 10 at. % in this structure and may enable a substitution of Tl with alkali metal atoms, in contrast to more Tl-rich chalcogenides such as Tl2NdAg3Se4,15 Tl9BiTe6,2 and Tl10−xSnxTe6 and Tl10−xPbxTe6.3 Thusly, both K2Ag12Se717 and K2Ag12Se7.1124 adopt similar yet different structures wherein the K atoms are also forming a linear chain of KSe6 trigonal prisms. Electronic Structure. Since there are no Se−Se contacts shorter than 4 Å, we can assign the typical oxidation states of Tl+, Ag+, and Se2−, resulting in the balanced formula (Tl+)2(Ag+)12(Se2−)7. Thus, the stoichiometric material appears to be an intrinsic semiconductor, which is confirmed by the density of states (DOS), presented in Figure 3, revealing a (calculated) band gap of 0.5 eV. It should be noted, however, that this calculation method usually results in smaller band gaps, compared to experimental methods.
Figure 4. DSC of Tl2Ag12Se7.
cooling rate, causing a delay in the onset of the phase transitions. The phase transition at 410 K causes major changes in the thermopower, α, namely, from p-type to n-type to p-type during heating, known as pnp conduction switching. The local minimum in the DSC curve (dotted line in Figure 5) corresponds nicely to the minimum in the Seebeck curve.
Figure 3. Density of states of Tl2Ag12Se7.
The states both above and below the Fermi level (dashed horizontal line) comprise Ag as well as Se contributions because of the covalent character of the Ag−Se interactions. The region between −3 and −6 eV is dominated by the (filled) Ag d states, while the Tl states have only negligible contributions, in part caused by the small amount of Tl in this material. The Tl-s states occur below the selected energy window. Physical Properties. Upon heating, two phase transitions are observed, namely, at 410 and at 710 K (Figure 4). The first reversible one (α−β) corresponds to a minor change in the crystal structure, as no obvious changes were identified in a powder diagram obtained at 453 K, and the latter likely corresponds to the melting point. A comparison with a previous phase diagram study of the Tl2Se−Ag2Se system implies that Tl2Ag12Se7 was originally identified as “TlAg7Se4”, which would incongruently melt into a more Tl-rich liquid and solid Ag2Se at 699 K.30 Upon fast cooling, one obtains Tl2Ag12Se7 and a small amount of “TlAg3Se2’, which explains the occurrence of a second crystallization peak. The shifts in the peak positions of the heating and cooling curves are a consequence of the fast
Figure 5. Seebeck coefficient and DSC of Tl2Ag12Se7.
After noting the changes from α = +194 μV K−1 at 402 K to −27 μV K−1 at 413 K, and then back up to +133 μV K−1 at 451 K in our first measurement (black squares in Figure 5), we collected more data in increments of ∼10 K on the same sample in the region of interest, in order to identify the corresponding maxima of both types (black triangles in Figure 5). This resulted in an abrupt change in α from +230 μV K−1 at 394 K to −227 μV K−1 at 414 K, and then back up to +76 μV K−1 at 423 K, proving the reversible character of the pnp switch. After the phase transition, α increases steadily to +305 μV K−1 at 586 K. The pnp switching behavior in the silver telluride−bromide Ag10Te4Br3 and its substitution variants was related to changes in the Te atom substructure.31 We note that the Se atoms of the two symmetry independent chains in Tl2Ag12Se7, Se4 and Se5, exhibit enlarged displacement parameters along the chain direction at room temperature. Moreover, the Se atoms of K2Ag12Se7.11 and the Te atoms of the related Tl4Ag24−xTe15−y 9568
DOI: 10.1021/acs.chemmater.7b04015 Chem. Mater. 2017, 29, 9565−9571
Article
Chemistry of Materials structure were published to be disordered over many deficient sites in a linear chain with various Se−Se and Te−Te distances < 3 Å.20 Thus, one might postulate that the chalcogen atom chains are responsible for the resistivity switching behavior in the case of this selenide as well, while our preliminary investigations showed no such change in the thermopower in the case of the thallium telluride. In contrast to the Seebeck curve, the electrical conductivity (σ) curve is inconspicuous, exhibiting more or less an exponential increase with increasing temperature, as predicted for an intrinsic, or slightly doped, semiconductor (Figure 6).
Figure 7. Thermal conductivity of Tl2Ag12Se7.
As is the case in the thermopower, the thermal conductivity also shows a peak during the phase transition, namely, a maximum of 0.44 W m−1 K−1 at 419 K, up from 0.36 W m−1 K−1 at 374 K. Thereafter, κ proceeds to gently decrease with increasing temperature because of the increasing lattice vibrations, down to 0.25 W m−1 K−1 at 578 K. Since the electrical conductivity remains small throughout this temperature range, the electronic contribution to the thermal conductivity is negligible. To assess the overall thermoelectric performance, the figureof-merit, zT = α2σTκ−1, needs to be determined. The larger zT is, the better is the thermoelectric performance; state-of-the-art materials exhibit zT values of 1 or higher. We determined a fit of the power factor PF = α2σ above the phase transition, to calculate zT at the temperatures of the κ measurement from the PF fit. While zT increases rapidly (Figure 8), even its maximum of 0.035 at 578 K is too low for the thermoelectric energy conversion, as expected based on the low electrical conductivity.
Figure 6. Electrical conductivity of Tl2Ag12Se7.
This implies that the charge carrier concentration remains low during the phase transition, while changing its dominant character from holes to electrons to holes. The σ values range from 0.04 Ω−1 cm−1 at 303 K to 2.0 Ω−1 cm−1 at 586 K. These values are too small for the thermoelectric energy conversion, where σ values of the order of several hundred Ω−1 cm−1 are required. On the other hand, the Seebeck values being above 200 μV K−1 for the most part of the measurement would be appropriate. The almost exponential temperature dependence of the electrical conductivity allows for an experimental estimation of the band gap, Eg, from the slope of the ln σ vs 1/T curve (Figure S2 in the Supporting Information). We obtained a linear fit with a regression coefficient of R2 = 0.999, and Eg = 0.8 eV. As expected, the experimental band gap is larger than the calculated one of 0.5 eV, while of the same order of magnitude. The thermal conductivity remains below κ = 0.45 W m−1K−1 during the whole data collection up to 578 K (Figure 7). These values are significantly lower than those of benchmark thermoelectric bulk materials such as Bi2Te3 and PbTe, and comparable to those of Tl-rich chalcogenides such as Tl9BiTe62 and Tl10−xSnxTe6 and Tl10−xPbxTe6.3 In this case, however, the Tl content is so small that the major driving force is the complexity of this structure, combined with partly deficient Ag sites and enlarged anisotropic displacement factors (ADPs, averaged to the Ueq values listed in Table 2), rather than the presence of Tl atoms. Specifically, the Se4 and Se5 atoms of the linear Se chains and their surrounding Ag sites, Ag2, Ag4, and Ag6, display larger ADPs than the other Se and Ag sites, respectively, while the Tl site is inconspicuous in contrast to Tl10−xSnxTe6 and Tl10−xPbxTe6.3
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CONCLUSION A new selenide, Tl2Ag12Se7, was discovered and characterized. It crystallizes in a supercell of the Zr2Fe12P7 type. We
Figure 8. Thermoelectric figure-of-merit of Tl2Ag12Se7. 9569
DOI: 10.1021/acs.chemmater.7b04015 Chem. Mater. 2017, 29, 9565−9571
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Chemistry of Materials
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determined this material to be a semiconductor with a very low thermal conductivity and, most notably, with reversible pnp switching behavior during its phase transition around 400 K. Interestingly, such a behavioras rare as that iswas earlier found in other silver chalcogenides, namely, in Ag10Te4Br3 and its substitution variants, materials that also exhibit a multitude of d10−d10 Ag−Ag interactions as well as a flexible chalcogen atom substructure. Further investigations into the mechanism of the phase transition will be undertaken, along with attempts to modify the pnp switching behavior by partial Se/Te substitution. Attempts to substitute thallium atoms with alkali metal atoms are underway, noting that the above-discussed K2Ag12Se7 and K2Ag12Se7.11 were so far only accessible via solvothermal methods using supercritical ethylenediamine. Despite the low thermal conductivity, the thermoelectric performance is insufficient because of the low electrical conductivity. Increasing the charge carrier concentration would be required to be able to obtain useful thermoelectric properties, in addition to replacing the Tl atoms to reduce the toxicity. In the future, we will also analyze the potential for ionic conductivity, although the Ag occupancies are all above 95% without very high displacement parameters, at least in the room temperature modification.
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ASSOCIATED CONTENT
S Supporting Information *
. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.7b04015. Figures displaying experimental powder diagrams and the logarithm of the electrical conductivity(PDF) Crystallographic information (CIF)
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AUTHOR INFORMATION
Corresponding Author
* E-mail:
[email protected]. ORCID
Holger Kleinke: 0000-0002-6777-6140 Present Address †
Materials Science and Technology Division and Academy of Scientific and Innovative Research (AcSIR), CSIR-National Institute for Interdisciplinary Science and Technology, Thiruvananthapuram 695019, Kerala, India. Funding
Financial support from the Natural Sciences and Engineering Research Council of Canada in the form of a Discovery Grant is appreciated. Notes
The authors declare no competing financial interest.
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